A new method for the synthesis of cyanohydroborates and cyanoborane complexes

Emri, J.; Győri, Béla

doi:10.1039/c39830001303

Cited by 17 publications

(27 citation statements)

References 2 publications

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“…The syntheses of salts of 2 and 3 known, so far, are summarized in Scheme . In 1983 the first syntheses for salts of both anions were reported . Na 3 ⋅2 dioxane was obtained starting from Na[BH 4 ] and Hg(CN) 2 .…”

Section: Introductionmentioning

confidence: 99%

“…[15,16] In 1983 the first syntheses for salts of both anions were reported. [10,12,[15][16][17][18][19][20][21][22] Na3·2 dioxanew as obtained startingfrom Na[BH 4 ]a nd Hg(CN) 2 . [16] Because of the byproducts mercury and HCN, this method is not applicable for the preparation of larger quantities of dicyanodihydridoborates.…”

Section: Introductionmentioning

confidence: 99%

“…[10,12,[15][16][17][18][19][20][21][22] Na3·2 dioxanew as obtained startingfrom Na[BH 4 ]a nd Hg(CN) 2 . [16] Because of the byproducts mercury and HCN, this method is not applicable for the preparation of larger quantities of dicyanodihydridoborates. AgCN was applieda sa na lternative CN source and reacted with Me 2 S·BH n Br 3Àn (n = 1, 2) to give the corresponding silver isocyanohydridoborates Ag[BH n (NC) 4Àn ].…”

Section: Introductionmentioning

confidence: 99%

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Cyanohydridoborate Anions: Synthesis, Salts, and Low‐Viscosity Ionic Liquids

Bischoff

Drisch

Kerpen

et al. 2019

Chemistry A European J

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High‐yield syntheses up to molar scales for salts of [BH(CN)3]− (2) and [BH2(CN)2]− (3) starting from commercially available Na[BH4] (Na5), Na[BH3(CN)] (Na4), BCl3, (CH3)3SiCN, and KCN were developed. Direct conversion of Na5 into K2 was accomplished with (CH3)3SiCN and (CH3)3SiCl as a catalyst in an autoclave. Alternatively, Na5 is converted into Na[BH{OC(O)R}3] (R=alkyl) that is more reactive towards (CH3)3SiCN and thus provides an easy access to salts of 2. Some reaction intermediates were identified, for example, Na[BH(CN){OC(O)Et}2] (Na7 b) and Na[BH(CN)2{OC(O)Et}] (Na8 b). A third entry to 2 and 3 uses ether adducts of BHCl2 or BH2Cl such as the commercial 1,4‐dioxane adducts that react with KCN and (CH3)3SiCN. Alkali metal salts of 2 and 3 are convenient starting materials for organic salts, especially for low viscosity ionic liquids (ILs). [EMIm]3 has the lowest viscosity and highest conductivity with 10.2 mPa s and 32.6 mS cm−1 at 20 °C known for non‐protic ILs. The ILs are thermally, chemically, and electrochemically robust. These properties are crucial for applications in electrochemical devices, for example, dye‐sensitized solar cells (Grätzel cells).

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Cyanohydridoborate Anions: Synthesis, Salts, and Low‐Viscosity Ionic Liquids

Bischoff

Drisch

Kerpen

et al. 2019

Chemistry A European J

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“…Salze mit dem [BH 3 CN] ± -Anion sind inzwischen gut untersucht [2±6] und werden in der organischen Synthese als selektive Reduktionsmittel eingesetzt [7]. In neuerer Zeit gelang die Einfu È hrung einer zweiten [3,8,9] und dritten [8] CN-Gruppe. Sowohl Na[BH n (CN) 4±n ] (n = 1, 2, 3) als auch Na[BH n (NC) 4±n ] (n = 1, 2) wurden 11 B-und 13 C-NMR spektroskopisch untersucht [6].…”

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Die Tetracyanoborate M[B(CN)4], M = [Bu4N]+, Ag+, K+

Bernhardt

Henkel

Willner

2000

Z. anorg. allg. Chem.

123

135

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“…[10] Further substitution of ac yano group with hydrogen leads to the anion[ BH 2 (CN) 2 ] À , which was first describedw ith main group elementc ations as counter ions. [9,11] Although the [BH 2 (CN) 2 ] À anion is also used as component of ionic liquids, [1a, 12] there is not much known abouti ts coordinationc hemistry besides the aforementioned compounds. As ubstitution of cyano groups is not restricted to hydrogena toms, but could also be accomplished with, for example, fluorine atoms [13] or perfluoralkyl groups.…”

Section: Introductionmentioning

confidence: 99%

Lanthanide Coordination Polymers and MOFs based on the Dicyanodihydridoborate Anion

Zottnick

Daul

Kerpen

et al. 2018

Chemistry A European J

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New lanthanide cyanoborates were synthesized from anhydrous lanthanide chlorides and the acid H[BH (CN) ] in either acetonitrile or pyridine. Reactions in acetonitrile lead to three-dimensional, anionic metal-organic frameworks (MOFs) [Ln {BH (CN) } ]⋅[Ln(CH CN) ] (Ln=Ce, Eu, Tb) which incorporate complex cations [Ln(CH CN) ] in the pores of the framework for charge compensation. In contrast, the reactions in pyridine result in the formation of one-dimensional coordination polymers [H(py) ][LnCl {BH (CN) } (py) ]⋅0.5 py (Ln=Ce, Pr, py=pyridine) with [H(py) ] as counter ions for the anionic strand structure. The products show intense photoluminescence, for Ce based on 5d-4f transitions in the blue spectral region, whereas the Eu and Tb compounds exhibit characteristic photoluminescence based on 4f-4f transitions of the respective lanthanide ions. The observed photoluminescence is mainly attributed to a direct excitation of the lanthanide ions and sensitization of the lanthanide ions by the [BH (CN) ] anions. These results mark the utilized borate anions as versatile building block for new coordination compounds.

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A new method for the synthesis of cyanohydroborates and cyanoborane complexes

Cited by 17 publications

References 2 publications

Cyanohydridoborate Anions: Synthesis, Salts, and Low‐Viscosity Ionic Liquids

Cyanohydridoborate Anions: Synthesis, Salts, and Low‐Viscosity Ionic Liquids

Die Tetracyanoborate M[B(CN)4], M = [Bu4N]+, Ag+, K+

Lanthanide Coordination Polymers and MOFs based on the Dicyanodihydridoborate Anion

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